Mixed higher polyoxyalkylene



Patented Mar. 30, 1954 I 1 i UNITED STATES PATENT OFFICE MIXED HIGHER POLYOXYALKYLENE ETHERS OF HEXITOLS William C. Griflin, West Chester, Pa., assignor to Atlas Powder Company, Wilmington, Del., a corporation of Delaware N Drawing. Application March 6, 1951, Serial No. 214,229

12 Claims. (01. 260-615) 1 2 The present invention relates to a composition tion. It is immaterial which of the alkylene of matter. More specifically it relates to high oxides is introduced first.

molecular weight mixed polyoxyalkylene ethers The following examples are cited to illustrate 01' hexitols. v the invention. They are not intended to limit An object of the present invention is to pro- 5 itinany way. vide new and useful high molecular weight mixed Example I polyoxyalkylene ethers of hexitols.

182 grams of dry crystalline sorbitol 1s charged Another (meet to proYlde method of m into an autoclave. The temperature is raised to pafrmg new and useful hlgh molecular Welght 140 C and the air above the molten sorbitol mlxed polyoxyalkylene ethers 9 heXitOls' is flushed with ethylene oxide. Agitation is These and other obJectS W f begun and 2.64 grams of sodium methylate cataent in the course of the following description. vlyst is added The pressure of the System is The mixed polyoxyalkylene ethers of hexitols creased to 40 by pumping in ethylene ide. of the class to be defined hereinafter have been The pressure maintained by t ethylene xide found of value as intermediates in the prepara- 15 Source until 2200 grams have been reacted The tion of organic compounds and are particularly feed is then changed to propylene oxide and valuable in the preparation of compounds for use the pressure maintained until 2900 grams have in the field of oil-water emulsion stratification. been reacted The resulting product represents They are also valuable as moisture conditioning i5o polyoxypropylene 5o polyoxyethylene and thickening agents. bitoL The novel mixed polyoxyalkylene ethers of hexi- Example H tols of the present invention may be represented by the following formula: loo-po y xypr pyl loo-p ly xv yl n sorbitol is prepared following the procedure of R([O(CH2)1]m[0(CH2) fl Example I employing 91 grams of sorbitol, 2.59 grams of sodium oleate as catalyst, 2200 grams wherem: of ethylene oxide and 2900 grams of propylene R is the residue of a hexitol; .r and y repre- OXldB- sent 2 or 3 and are of different values; m and n Example HI each represents an integer above 6 and preferably 200-poly0xypropy1ene, 200-polyoxyethylene below about and the ratio of mm lies within sorbitol is prepared following th procedure of the limits of from 31 t0 Example I employing 91 grams of sorbitol, 5.14 es Compounds are p p y Separate and grams of sodium ethoxide as catalyst, 4400 grams subsequent etherification of a hexitol with the of ethylene oxide and 5800 grams of propylene desired proportions of each of ethylene and 1,2 35 d P py OXidBS- The reaction between the The etherification may also be performed using one P Y and alkylene OXide Will DITXBBEQ1 at an aqueous solution of the polyol. In this event, mosp c pressure even Subatmospherlc P a portion of the added alkylene oxide is consumed sure, without any ad e s ts p y by in the production of polyglycols. To attain the addition of the y e OXide t0 the P Y at necessary oxyalkylene chain length under such a temperature in eXcesS of about conditions this factor must be considered and ever, it has been found advisable to operate unappropriate compensation made, For use in der a superatmospheric pressure and in the presemulsion breaking, separation from the polyence of an alkaline catalyst such as caustic soda, glycols has not been found necessary. Derivasoda ash, salts of strong alkalies and weak bases 5 tives formed from polyols containing as much as such as sodium acetate and the like, which per- 15% water have been found satisfactory.

mits etherification at a lower temperature. The Example IV on enientl erformed gfggfg g igg igg i f m 1 5 to 182 grams of dry crystalline sorbitol is charged C under a pressure of fr 30 to in 50 into an autoclave. The temperature is raised to the presence of from 0.05 to 0.5% catalyst based 1 the the o e sqrbltol is flushed with ethylene oxide. Agitation 1S begun on total charge. Prior to the reaction the atmosphere within the reactor is flushed with alkylene and grams of sodlum methylate catalyst is oxide or an inert gas. Thorough agitation is F1 are indicates aver-a e number of polyoxyalkylena constantly provided during the course of the reac- 55 noupfper new g Y added. The pressure is increased to 40 p. s. i. by pumping in ethylene oxide. The pressure is maintained over the range of 30-40 p. s. i. until 2200 grams of ethylene oxide have reacted. The gas 2. The compound of claim 1 wherein A1 is the alkylene radical of ethylene oxide.

3. The compound of claim 1 wherein A1 is the alkylene radical of 1,2-propylene oxide.

feed is then changed to 1,2 propylene oxide and 5 4. The compound of claim 2 wherein the prodthe pressure maintained within the range until ucts 6m and 61 are each 50. 8700 grams have reacted. The product is 150- 5. The compound of claim 2 wherein the prodpolyoxypropylene, 50-polyoxyethylene sorbitol. ucts 6m and (in are each 100 The following example illustrates the produc- 6. The compound of claim 2 wherein the prodtion of a mixed polyoxyalkylene hexitol by etheril0 ucts 6m and 611. areeach 200. fication in the presence of 12% water. 7. The compound of claim 2 wherein the prod- Example V uct 6m is 50 and the product 611. is 100.

V 8. The compound of claim 2 wherein R is the A 22 gram sample of sorbitol containing 12% mannitol residue. water is reacted in accordance with the procedure 15 9. The compound of claim 3 wherein the prodof Example I with 733 grams of ethylene oxide uct 6m and the product 6n are each 100. and 966 grams of propylene oxide using 1.72 10. The compound of claim 4 wherein R. is the grams of sodium methylate as catalyst. The sorbitol residue. product is a polyglycol solution of 100-polyoxy- 11. The compound of claim 5 wherein R is the propylene, 100-polyoxyethylene sorbitol. sorbitol residue.

Othermodifications of this class of mixed poly- 12. The compound of claim 6 wherein R is oxyethylene ethers of hexane polyols are prethe sorbitol residue. pared as follows: WILLIAM C. GRIFFIN.

Example $21??? Alkylene Oxides Catalyst Product VI 91 grams of 5, 800 gr. Pro; 2,200 gnEtO. 5.2 grams of 100-polyoxyethylene;200-poly0xypromannitol. caustic soda. pylene mannitol. VII 36.4 gr. dul- 812 gr. PrO; 1,760 gr. Et0 2.6 grams of zoo-polyoxyethyleue; 70-po1yoxyprocitol. soda ash. pylene ducitol. VIII 91 grams of 2,900 gr. PrO; 2,200 gr. Et-O'". 5.2 grams of loo-polyoxyethylene;ioo-polyoxyprosorbitol. methpylene sorbitol.

* Indicates 1,2 propylene oxide. Indicates ethylene oxide.

It will be apparent to those skilled in the art that many variations of the above disclosures are possible without departing from the scope of the invention.

What is claimed is:

1. A compound of the formula:

wherein R is the residue of a hexitol, A1 and A2 represent, respectively, alkylene radicals of different 1,2-alkylene oxides containing no more than 3 carbon atoms, m and 12 each represent a number above 6, and the ratio of mm lies within the limits 1:3 to 3:1.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 40 1,922,459 Schmidt et al Aug. 15, 1933 2,481,278 Ballard et a1 Sept. 6, 1949 2,549,435 De Groote et al Apr. 1'7, 1951 2,552,528 De Groote May 15, 1951 2,552,529 De Groote May 15, 1951 FOREIGN PATENTS Number Country Date 616,256 Great Britain Jan. 19, 1949 

1. A COMPOUND OF THE FORMULA: 